Enamel for coating steel articles
An enamel for coating steel articles is disclosed comprising SiO.sub.2, Tsub.2, ZrO.sub.2, CaF.sub.2, LiO and Na.sub.2 O with the following ratio of the components, in percent by weight:______________________________________ SiO.sub.2 62.17 to 72.29 TiO.sub.2 0.2 to 9.54 ZrO.sub.2 0.5 to 9.9 CaF.sub.2 2.4 to 6.6 Li.sub.2 O 0.3 to 5.06 Na.sub.2 O 10.48 to 19.05 ______________________________________The enamel may also comprise Cr.sub.2 O.sub.3 or Co.sub.2 O.sub.3 in an amount of 0.5 to 2 percent by weight. The oxides ensure the preparation of an enamel of a green or blue color, respectively. The enamel efficiently protects steel articles from aggressive media, i.e. acids and alkalis and the enamel coating has good luster and high continuity, without pinholes.
The present invention relates to enamels for coating steel articles with a view to afford protection to same from the effect of aggressive media such as acids and alkalis. The aforesaid steel articles can be pipes, reactors, heat exchangers and other vessels.
The prior art teaches an enamel for coating steel articles comprising SiO.sub.2, Al.sub.2 O.sub.3, CaO, Na.sub.2 O, K.sub.2 O, B.sub.2 O.sub.3, TiO.sub.2, Li.sub.2 O, ZrO.sub.2, CaF.sub.2, CuO and SrO with the following ratio of said components, in percent by weight:
______________________________________ SiO.sub.2 50 to 80 Al.sub.2 O.sub.3 0.5 to 6 CaO 0.2 to 5 Na.sub.2 O 7 to 20 K.sub.2 O up to 5 B.sub.2 O.sub.3 0.2 to 6 TiO.sub.2 up to 5 Li.sub.2 O 0.2 to 5 ZrO.sub.2 0.2 to 10 CaF.sub.2 0.2 to 7 CuO 0.5 to 20 SrO 0.2 to 10 ______________________________________
The disadvantages of the enamel known in the art are the use of a large number of components, as well as a large amount of copper oxide which may result in metallization of the coating and deterioration of its protective properties. In addition, copper oxide is toxic.
SUMMARY OF THE INVENTIONIt is an object of the present invention to prepare such enamel for coating steel articles which would comprise a considerably smaller number of components and would not require critical and toxic materials for its preparation, having at the same time high protective properties.
In accordance with the foregoing and other objects of the invention, there is proposed an enamel for coating steel articles comprising SiO.sub.2, TiO.sub.2, ZrO.sub.2, CaF.sub.2, Li.sub.2 O and Na.sub.2 O with the following ratio of said components, in percent by weight:
______________________________________ SiO.sub.2 62.17 to 72.29 TiO.sub.2 0.2 to 9.54 ZrO.sub.2 0.5 to 9.9 CaF.sub.2 2.4 to 6.6 Li.sub.2 O 0.3 to 5.06 Na.sub.2 O 10.48 to 19.05 ______________________________________
DESCRIPTION OF THE PREFERRED EMBODIMENTSThe enamel of the invention differs from known enamel in that it comprises half as many components and does not contain the critical boron oxide and toxic copper oxide. The enamel has a high acid resistance and alkali resistance and makes it possible to prepare a high-quality coating, without pinholes.
It is recommended to use an enamel having the following composition, in percent by weight:
______________________________________ SiO.sub.2 68.0 TiO.sub.2 3.23 ZrO.sub.2 4.95 CaF.sub.2 6.32 Li.sub.2 O 2.5 Na.sub.2 O 15.0 ______________________________________
The enamel of said composition has the highest acid and alkali resistance and forms the highest-quality coating (continuous, without pinholes) on steel articles.
The enamel may contain in its composition such components as Cr.sub.2 O.sub.3 or Co.sub.2 O.sub.3 in an amount of 0.5 to 2 percent by weight. The oxides make it possible to produce the enamel of a green blue color, respectively.
The proposed enamel is prepared in the following manner.
First a batch is prepared, the batch components being the following substances:
(1) silica sand or pure silicon dioxide;
(2) titanium dioxide;
(3) zircon concentrate ZrSiO.sub.4 ;
(4) fluorspar;
(5) lithium carbonate;
(6)soda.
The content of the components in the batch is determined by the content of oxides in the enamel.
The batch components are proportioned, mixed and completely melted in rotary or hearth-type furnaces at a temperature of 1,300.degree. to 1,350.degree. C. The melted enamel is fritted by pouring it in to water or passing through rolls. Thereafter the fritted enamel is dried at a temperature of 100.degree. to 120.degree. C. and a dross is prepared. For this purpose the fritted enamel is charged into a ball mill adding thereto clay in an amount of 5 to 7 percent by weight of the frit, an electrolyte such as ammonium chloride and or ammonium molybdate and molybdenum anhydride, in an amount of 0.5 to 1 percent by weight of the frit, chromium oxide or cobalt oxide, if necessary, in an amount of 0.5 to 2 percent by weight of the frit, and water in an amount of 40 to 50 percent by weight of the frit. The resultant mass is subjected to grinding to a requisite fineness, e.g. that of 1.4 to 1.7 cm (by the method of settling in a Lisenko cylinder).
The prepared dross is applied to pre-primed steel articles by a method of dipping or spraying and the enamel coating is dried at a temperature of 20.degree. to 120.degree. C. The dried coating is subjected to calcination at a temperature of 820.degree. to 860.degree. C. in electric furnaces or in induction units.
For obtaining a continuous (without pinholes) enamel coating it is necessary to apply the dross to the articles at least three times, drying and calcining the coating after each application.
For a better understanding of the present invention the following examples of producing the proposed enamel are given.
EXAMPLE 1A batch of the following composition is prepared as calculated per 100 parts by weight of the enamel:
______________________________________ silica sand 59.84 titanium dioxide 9.54 zircon concentrate ZrSiO.sub.4 7.28 fluorspar 6.21 lithium carbonate 5.88 soda 25.31 114.06 ______________________________________
The batch components are proportioned, mixed and melted in a rotary furnace at a temperature of 1,300.degree. to 1,320.degree. C. till complete melting thereof. The melted enamel is fritted by pouring it in to water. Thereafter the fritted enamel is dried at a temperature of 100.degree. to 120.degree. C. and a dross is prepared. For this purpose there are charged into a ball mill 100 parts by weight of the enamel frit, 5 parts by weight of clay, one part by weight of ammonium molybdate, and 42.0 parts by weight of water. The resultant mass is subjected to grinding to a requisite fineness, e.g. that of 1.4 cm (by the method of settling in a Lisenko cylinder).
The prepared dross is applied to pre-primed steel articles and the enamel coating is dried at a temperature of 20.degree. C. to 120.degree.. The dried coating is calcined in an electric furnace at a temperature of 860.degree. C.
For obtaining a continuous (without pinholes) enamel coating the dross is applied to the articles three times, drying and calcining the coating after each application.
The resultant coating (enamel) has the following composition, in percent by weight:
______________________________________ SiO.sub.2 62.17 TiO.sub.2 9.54 ZrO.sub.2 4.9 CaF.sub.2 6.21 Li.sub.2 O 2.38 Na.sub.2 O 14.8 100 ______________________________________ Physical and chemical characteristics of the enamel: ______________________________________ coeffiecient of linear expansion (.alpha.), in degrees.sup.-1 87.10.sup.-7 calcination range, in .degree.C. 845 to 915 heat resistance, in .degree.C. 200 leachability, in mg/cm.sup.2,of the enamel coating after keeping a steel article with a coating for four hours in boiling aqueous solutions: (1) a 20, 24% aqueous solution of hydrochloric acid 0.11 (2) a 2 N aqueous solution of so- dium hydroxide 0.47 ______________________________________
The resultant enamel coating has a light gray color and is distinguished by good luster and high continuity.
EXAMPLE 2The preparation of the enamel and its application to steel articles is carried out in a manner similar to that set forth in Example 1.
The patch composition, in parts by weight (as calculated per 100 parts by weight of the enamel):
______________________________________ silica sand 60.18 titanium dioxide 0.2 zircon concentrate 14.72 fluorspar 5.7 lithium carbonate 5.85 soda carbonate 25.27 111.92 ______________________________________
The dross composition, in parts by weight:
______________________________________ enamel frit 100 clay 7 ammonium chloride 0.5 chronium oxide Cr.sub.2 O.sub.3 2 water 50 158.5 ______________________________________
The enamel composition, in percent by weight:
______________________________________ SiO.sub.2 65.05 TiOI.sub.2 0.2 ZrO.sub.2 9.9 CaF.sub.2 5.7 Li.sub.2 O 2.37 Na.sub.2 O 14.78 Cr.sub.2 O.sub.3 2 100 ______________________________________ Physical and chemical characteristics of the enamel: ______________________________________ coefficient of linear expansion (.alpha.), in degrees.sup.-1 102.10.sup.- calcination range, in .degree. C. 840 to 900 heat resistance, in .degree.C. 210 leachability, in mg/cm.sup.2, of the enamel coating after keeping a steel article with a coating for four hours in boiling aqueous so- lutions: (1) a 20, 24% aqueous solution of hydrochloric acid 0.13 (2) a 2N aqueous solution of so- dium hydroxide 0.48 ______________________________________
The resultant enamel coating has a green colour and good luster and high continuity.
EXAMPLE 3The preparation of the enamel and its application to steel articles is carried out in a manner similar to that set forth in Example 1.
The batch composition, in parts by weight (as calculated per 100 parts by weight of the enamel):
______________________________________ silica sand 57.86 titanium dioxide 6.25 zircon concentrate 13.64 fluorspar 2.40 lithium carbonate 0.74 soda 32.57 113.46 ______________________________________
The dross composition, in parts by weight:
______________________________________ enamel frit 100 clay 5 ammonium chloride 0.1 ammonium molybdate 0.2 molybdenum anhydride 0.4 chromium oxide Cr.sub.2 O.sub.3 0.5 water 47.0 153.2 ______________________________________
The enamel composition, in percent by weight:
______________________________________ SiO.sub.2 62.33 TiO.sub.2 6.25 ZrO.sub.2 9.17 CaF.sub.2 2.40 Li.sub.2 O 0.3 Na.sub.2 O 19.05 Cr.sub.2 O.sub.3 0.5 100 ______________________________________ Physical and chemical characteristics of the enamel: ______________________________________ coefficient of linear expansion (.alpha.), in degrees.sup.-1 95.10.sup.-7 calcination range, in .degree. C. 830 to 900 heat resistance, in .degree. C. 200 leachability, in mg/cm.sup.2, of the enamel coating after keeping a steel article with a coating for four hours in boiling aqueous solu- tions: (1) a 20, 24% aqueous solution of hydrochloric acid 0.12 (2) a 2N aqueous solution of sodium hydroxide 0.45 ______________________________________
The resultant enamel coating has a light green colour and good luster and high continuity.
EXAMPLE 4The preparation of the enamel and its application to steel articles is carried out in a manner similar to that set forth in Example 1.
The batch composition, in parts by weight (as calculated per 100 parts by weight of the enamel):
______________________________________ silica sand 72.05 titanium dioxide 2.32 zircon concentrate 0.74 fluorspar 6.48 lithium carbonate 6.13 soda 26.38 114.10 ______________________________________
The dross composition, in parts by weight:
______________________________________ enamel frit 100 clay 6.0 ammonium chloride 0.5 cobalt oxide Co.sub.2 O.sub.3 0.5 water 40 147 ______________________________________
The enamel composition, in percent by weight:
______________________________________ SiO.sub.2 72.29 TiO.sub.2 2.32 ZrO.sub.2 0.5 CaF.sub.2 6.48 Li.sub.2 O 2.48 Na.sub.2 O 15.43 Co.sub.2 O.sub.3 0.5 100 ______________________________________ Physical and chemical characteristics of the enamel: ______________________________________ coefficient of linear expan- sion (.alpha.), in degrees.sup.-1 99.10.sup.-7 calcination range, in .degree. C. 845 to 915 heat resistance, in .degree. C. 220 leachability, in mg/cm.sup.2, of the enamel coating after keeping a steel article with a coating for hours in boiling aqueous solutions: (1) a 20, 24% aqueous solution of hydrochloric acid 0.09 (2) a 2N aqueous solution of sodium hydroxide 0.47 ______________________________________
The resultant enamel coating has a light blue color and good luster and high continuity.
EXAMPLE 5The preparation of the enamel and its application to steel articles is carried out in a manner similar to that set forth in Example 1.
Composition of the batch, in parts by weight (as calculated per 100 parts by weight of the enamel):
______________________________________ silica sand 65.59 titanium dioxide 3.23 zirconium concentrate 7.36 fluorspar 6.32 lithium carbonate 6.20 soda 25.65 114.35 ______________________________________
Composition of the dross, in parts by weight:
______________________________________ enamel frit 100 clay 5 molybdenum anhydride 0.5 ammonium chloride 0.5 water 45 151.0 ______________________________________
Composition of the enamel, in percent by weight:
______________________________________ SiO.sub.2 68.0 TiO.sub.2 3.23 ZrO.sub.2 4.95 CaF.sub.2 6.32 Li.sub.2 O 2.5 Na.sub.2 O 15.0 100 ______________________________________ Physical and chemical characteristics of the enamel: ______________________________________ coefficient of linear expansion (.alpha.), in degrees.sup.-1 98.10.sup.-7 calcination range, in .degree. C. 800 to 920 heat resistance, in .degree. C. 250 leachability, in mg/cm.sup.2, of the enamel coating after keeping a steel article with a coating for four hours in boiling aqueous solutions: (1) a 20,24% aqueous solution of hydrochloric acid 0.06 (2) 1 2N aqueous solution of sodium hydroxide 0.42 leachability, in mg/cm.sup.2, of the enamel coating after its consecu- tive treatment with a 20,24% aqueous solution of hydrochloric acid and a 2N aqueous solution of sodium hydro- xide at a temperature of 96.degree. C. and with the duration of each treatment of three hours; said treatment cycles "acid-alkali" are conducted 6 times 3.7 ______________________________________
The resultant enamel was tested for acid resistance according to JTE/13 in liquid and vapor phases of 20,24% aqueous solution of hydrochloric acid at the solution boiling temperature for 48 hours. The results of the test are given in Table 1.
Table 1 ______________________________________ Leachability of the enamel g Test medium mg/cm.sup.2 m.sup.2 .multidot. day mm/year ______________________________________ Liquid phase 0.13 0.65 0.09 Vapor phase 0.20 1.00 0.14 ______________________________________
The enamel was also tested for alkali resistance according to DIN/51156 in a 4% aqueous solution of sodium hydroxide at a temperature of 80.degree. C. for 48 hours. The test results are given in Table 2.
Table 2 ______________________________________ Leachability of the enamel g mg/cm.sup.2 m.sup.2 .multidot. day mm/year ______________________________________ 0.44 2.2 0.32 ______________________________________
The resultant enamel has a light gray colour with addition of 1 wt. % of Cr.sub.2 O of light green colour, and 0.5 wt.% of light blue colour and good luster and high continuity.
EXAMPLE 6The preparation of the enamel and its application to steel articles is conducted in the same way as in Example 1.
Composition of the batch, in parts by weight (as calculated per 100 parts by weight of the enamel):
______________________________________ silica sand 70.36 titanium dioxide 6.76 zircon concentrate 0.74 fluorspar 6.6 lithium carbonate 12.5 soda 17.35 114.31 ______________________________________
Composition of the dross, in parts by weight:
______________________________________ enamel frit 100 clay 5.5 ammonium chloride 0.5 water 42.5 148.5 ______________________________________
Composition of the enamel, in percent by weight:
______________________________________ SiO.sub.2 70.60 TiO.sub.2 6.76 ZrO.sub.2 0.5 CaF.sub.2 6.6 Li.sub.2 O 5.06 Na.sub.2 O 10.48 100 ______________________________________ Physical and chemical characteristics of the enamel: ______________________________________ coefficient of linear expansion (.alpha.), in degrees.sup.-1 90.10.sup.-7 Calcination range, in .degree. C. 840 to 910 heat resistance, in .degree. C. 210 leachability, in mg/cm.sup.2, of the enamel coating after keeping a steel article with a coating for four hours in boiling aqueous so- lutions: (1) a 20, 24% aqueous solution of hydrochloric acid 0.11 (2) a 2N aqueous solution of sodium hydroxide 0.43 ______________________________________
The resultant enamel has a light gray colour (with addition of 1 wt.% of Cr.sub.2 O.sub.3 of light green colour, and 0.5 wt.% of light blue colour) and good luster and high continuity.
EXAMPLE 7The preparation of the enamel and its application to steel articles is conducted in the same way as in Example 1.
Composition of the charge, in parts by weight (as calculated per 100 parts by weight of the enamel):
______________________________________ silica sand 67.95 titanium dioxide 1.53 zircon concentrate 9.37 fluorspar 3.2 lithium carbonate 10.29 soda 21.72 114.06 ______________________________________
Composition of the dross, in parts by weight:
______________________________________ enamel frit 100 clay 6 ammonium chloride 0.1 ammonium molybdate 0.2 molybdate anhydride 0.4 cobalt oxide Co.sub.2 O.sub.3 1.0 water 47.0 154.7 ______________________________________
Composition of the enamel, in percent by weight:
______________________________________ SiO.sub.2 71.10 TiO.sub.2 1.53 ZrO.sub.2 6.3 CaF.sub.2 3.2 Li.sub.2 O 4.17 Na.sub.2 O 12.7 Co.sub.2 O.sub.3 1.0 100 ______________________________________ Physical and chemical characteristics of the enamel: ______________________________________ coefficient of linear expansion (.alpha.), in degrees.sup.-1 93.10.sup.-7 calcination range, in .degree. C. 840 to 900 heat resistance, in .degree. C. 200 leachability, in Mg/cm.sup.2, of the enamel coating after keeping a steel article with a coating for four hours in boiling aqueous solutions: (1) a 20,24% aqueous solution of hydrochloric acid 0.12 (2) a 2N aqueous solution of sodium hydroxide 0.43 ______________________________________
The resultant enamel coating has a blue colour and good luster and high continuity.
Claims
1. An enamel composition for coating steel articles, consisting essentially of comprising SiO.sub.2, TiO.sub.2, ZrO.sub.2, CaF.sub.2, Li.sub.2 O and Na.sub.2 O with the following ratio of said components, in percent by weight:
2. An enamel composition according to claim 1, consisting essentially of SiO.sub.2, TiO.sub.2, ZrO.sub.2, CaF.sub.2, Li.sub.2 O and Na.sub.2 O with the following ratio of said components, in percent by weight:
3. An enamel composition according to claim 1, which further includes a metal oxide selected from the group consisting of Cr.sub.2 O.sub.3 and Co.sub.2 O.sub.3 in an amount of 0.5 to 2 percent by weight.
| 2010776 | August 1935 | Frost |
| 2347187 | April 1944 | Frost |
| 3098753 | July 1963 | Van Dolah et al. |
| 3365315 | January 1968 | Beck |
| 3507687 | April 1970 | Laird |
| 3556821 | January 1971 | Hanzlik |
| 3836373 | September 1974 | Ault et al. |
| 3861926 | January 1975 | Irlam |
| 3969121 | July 13, 1976 | Atkinson |
Type: Grant
Filed: Mar 2, 1977
Date of Patent: Mar 18, 1980
Assignee: Institut Obschei i Neorganicheskoi Khimii Akademii Nauk Belorusskoi SSR
Inventors: Lev G. Khodsky (Minsk), Alla I. Brazgovskaya (Minsk), Valentina S. Kaminskaya (Minsk), Evgeny N. Podkletnov, deceased (late of Moscow)
Primary Examiner: O. R. Vertiz
Assistant Examiner: Mark Bell
Attorneys: Robert E. Burns, Emmanuel J. Lobato, Bruce L. Adams
Application Number: 5/773,753
International Classification: C03C 304; C03C 702;
